次甲基蓝-Mn2+-H2O2体系光度法测定中药的抗氧化性

提出了Mn^2 -H2O2一次甲基蓝分析新体系并用于羟自由基的测定：醋酸介质中,用Mn^2 与RQ反应,类似Fenton试剂产生羟自由基,羟自由基与次甲基蓝反应,使次甲基蓝褪色,用分光光度汁测定其吸光度的变化(△A664),可间接测定羟自由基的产生量．实验结果表明．△A664与次甲基蓝、MnSO4及H2O2呈量效关系．中药提取物可以清除溶液中的羟自由基,使次甲基蓝溶液的褪色程度降低,据此建立了一种测定中药对羟自由基清除率的新方法．测定了五倍子、诃子、金银花等11种中药的抗氧化性,结果满意。     

考马斯亮蓝G250褪色光度法测定Fenton反应产生的羟基自由基

在约0.008 mol.L-1硫酸介质中,Fenton反应产生的羟基自由基可使考马斯亮蓝G250(CBB G250)显著褪色。在CCB G250的吸收峰582 nm波长处测得的吸光度降低值(ΔA)与羟自由基(.OH)浓度在25 mg.L-1以下的范围内呈线性关系。根据Fenton反应及与方程式所示的化学计量关系,可用过氧化氢的浓度代表羟自由基浓度。用过氧化氢标准溶液对此反应体系作精密度试验,测得相对标准偏差(n=6)为0.6%。应用此方法对抗坏血酸等9种抗氧化剂的清除羟基自由基性能进行了测定。结果表明此方法可方便地应用于抗氧化剂的筛选。     

褪色光度法测定芬顿体系中产生的羟自由基

建立了检测Fenton反应产生羟自由基的新方法。在pH3．5条件下，经自由基与甲基紫发生反应使甲基紫褪色，在580nm处用分光光度计测定其△A值的变化，可间接测定羟自由基的生成量。通过对测定条件的研究，得到最佳实验条件。甲基紫光度法稳定性好，可作为一种简便的筛选羟自由基清除剂的方法。     

胭脂红酸褪色光度法检测H2O2-Fe2+产生的羟自由基

提出了Fe2 H2O2 胭脂红酸分析新体系,并用于羟自由基的测定。该法用Fenton反应产生羟自由基,并加入胭脂红酸显色剂,使胭脂红酸褪色,采用分光光度计测定其ΔA值的变化,可间接测定羟自由基的产生量。通过测定条件的研究,得出最佳实验条件,并对抗坏血酸等7种抗氧化剂的抗羟自由基氧化性能进行了比较。     

褪色光度法测定羟自由基及常见食物的抗氧化活性

在用稀硫酸调节至pH 4的溶液中,生物染色剂玫瑰桃红R能被由Fenton反应产生的羟自由基(·OH)氧化而褪色.根据在520 nm波长处所测得的吸光度的消褪的程度(△A=A0-A1),实现了羟自由基存在量的光度测定,应用此方法还测定了自由基消除率,作为选择清除剂的判据;还测定了几种常见食品的抗氧化活性.从方法的操作和所测得的结果证明该方法具有操作简单、方便且稳定而经济.     

药用百合提取液对羟自由基清除作用的研究

在Fenton反应产生羟自由基的稳定体系中,以溴邻苯三酚红为显色剂,用分光光度法测定吸光度的变化值,研究百合提取液在此体系中清除羟自由基的作用。通过常见抗氧化剂对羟自由基清除作用的对照试验表明,百合提取液对羟自由基有较好的清除效果,此法操作简便,稳定性好,测定快速,为开发百合复方保健品提供理论依据。     

亮绿褪色光度法检测Fenton反应产生的羟自由基

建立了Fg^2＋-H2O2-亮绿的分析新体系，并用于羟自由基的检测。该法利用Fenton反应产生羟自由基，并加入亮绿显色剂，羟自由基使亮绿褪色。在632nm处测其△A值的变化，可间接测定羟自由基的产生量。探讨了最佳实验条件，并对苯甲酸与丹参等中草药的抗羟自由基氧化性能作了比较，以验证本法的有效性，得到较好的清除结果。该法稳定，可作为一种简便的筛选抗氧化剂的方法。     

不同提取方法对红茶提取物抗氧化活性影响的研究

采取沸水浴法、回流法、微波法及超声波法探讨信阳红茶和印度红茶的抗氧化性,通过测定吸光度利用Fenton反应表征提取物对羟自由基的清除率.不同的提取方法对红茶抗氧化活性有一定的影响,羟自由基的清除率与红茶的抗氧化活性成正比.结果表明:信阳红茶沸水浴法提取率较高,印度红茶超声波法提取率较高.     

水杨基荧光酮荧光法测定钴（II）—过氧化氢系产生的羟自由基

本实验发现Co^2 与H2O2反应生羟自由基的产率比Fenton试剂的高100倍以上,采用水杨基荧光酮(salicyfluorone,SAF)-Co(II)-H2O2荧光法测定羟自由基的新体系,激发波长和发射波长为510nm和500nm,测定体系在反应前后的荧光变化,可间接测定羟自由基产生量,此法不需昂贵的仪器设备,方法灵敏,操作简单易行,清除率实难及ESR波谱法检测证明了该方法的准确可靠,对于医用筛选抗羟自由基药物及抗羟自由基机理研究等方面应用价值.     

褪色光度法测定Fenton反应产生的羟自由基及其应用

建立检测Fenton反应产生羟自由基的新方法。Fenton反应产生的羟自由基与苋菜红反应，颜色发生变化，用分光光度计测定其△A510值的变化，可间接测定羟自由基的生成量。通过对测定条件的研究，确定了体系最佳实验条件。抗氧化药物甘露醇、硫脲与羟自由基清除率具有明显的量效关系。测定了阿魏酸、芦丁等几种中药活性成分清除羟自由基的功能，此法可用于羟自由基清除剂的筛选及抗羟自由基机理研究。     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.     

Synthesis of N-substituted carbazolones from α-iodo enaminones via Pd(0)-catalyzed intramolecular coupling under microwave irradiation

A variety of N-aryl and N-alkyl carbazolones were conveniently achieved in good to high yields via Pd₂(dba)₃-mediated intramolecular coupling of N-substituted α-iodo enaminones under microwave irradiation. The Pd(0)-catalyzed cyclization was found to proceed favorably with the more electron-deficient phenyl ring during the reactions involving unsymmetrical N,N-diaryl α-iodo enaminones. This unique property enables the construction of carbazolone skeleton containing nitro substituted benzenoid ring.     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles by intramolecular nitrilimine cycloaddition

Both substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles have been synthesized by the 3+2 intramolecular dipolar cycloaddition of nitrilimines to alkynes. This cyclization has been extended to more versatile 3-bromo derivatives by the use of alkynylbromides as dipolarophiles.